Compatibilized blends of non-polar thermoplastic elastomers and polar thermoplastic polymers

ABSTRACT

The invention relates to compatibilized blends comprising 
     a non-polar thermoplastic elastomer, 
     a polar thermoplastic polymer selected from thermoplastic polyurethane (TPU), chloro containing polymers, fluoro containing polymers, polyesters, acrylonitrile-butadiene-styrene copolymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymer, polyacetal, polycarbonate, polyphenylene oxide, and 
     a suitable compatibilizer.

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to compatibilized blends of non-polarpolyolefinic thermoplastic elastomers and polar thermoplastic polymerswhich have been compatibilized by a suitable compatibilizer.Furthermore, the present invention relates to shaped articles consistingof said compatibilized blends.

The concept of using compatibilizers as interfacial agent in polymerblends is almost as old as the polymers themselves. For a detailedbackground information it is referred to: “Polymer Blends” by D. R. Pauland S. Newman, Volume 1, 2, Academic Press, Inc., 1978.

As widely described in the literature, a remarkable balance of diverseproperties is achievable with blends of different polymers, providedthat a suitable stability of the morphology between the differentpolymeric ingredients of the blend is achieved.

The object of the present invention is to provide blends of specificpolymers which, under normal circumstances, would be incompatible witheach other, and consequently their blends show poor physical propertiesor in many cases they can not or can only hardly be blended, mixed orotherwise processed. In detail, it is an object of the present inventionto provide compatibilized blends of non-polar thermoplastic elastomerswith polar thermoplastic polymers thus achieving improved properties ofthe final product blend which resemble the properties of both componentsin the blends.

For instance, polyvinylidene fluoride (PVDF) is an inert flexiblethermoplastic which is known for its excellent resistance to chemicalsand fluids and its abrasion resistance. Furthermore, PVDF has a highservice temperature and a low surface coefficient of friction. Anotherexample for thermoplastic polymer would be thermoplastic urethanes (TPU)which are known for their bonding to different polar substrates such asABS, PVC, etc., its paintability, abrasion resistance and gloss. Both,PVDF and TPU are incompatible with non-polar thermoplastic elastomers,i.e., they do not form homogeneous blend nor can they be satisfactorilyprocessed. The overall physical properties of such incompatible “blends”are poor.

The same situation is faced when an attempt is made to blend the polarpolyvinylidene chloride (PVDC), polyvinyl chloride (PVC) or polyesterswith the non-polar thermoplastic elastomers.

The object of the present invention has surprisingly been solved by theaddition of a suitable compatibilizer to the blend comprising thenon-polar thermoplastic elastomer and the polar thermoplastic polymers.

A further object of the present invention is the provision of acompatibilized blend of non-polar thermoplastic elastomers with polarthermoplastic polymers showing good adhesion to polar substrates, inparticular to polar polymeric substrates.

DESCRIPTION OF THE INVENTION

In detail the present invention relates to a compatibilized blendcomprising

a non-polar thermoplastic elastomer,

a polar thermoplastic polymer selected from thermoplastic polyurethane(TPU), chloro containing polymers, fluoro containing polymers,polyesters, acrylonitrile-butadiene-styrene copolymers,styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymer,polyacetal, polycarbonate, polyphenylene oxide, and

a compatibilizer.

The compatibilized blends of the present invention comprise

50 to 98% by weight, preferably 60 to 95% by weight, most preferably 70to 90% by weight of the non-polar thermoplastic elastomer,

50 to 2% by weight, preferably 40 to 5% by weight, most preferably 30 to10% by weight of the polar thermoplastic polymer,

based on the total amount of the non-polar thermoplastic elastomer(s)and the polar hermoplastic polymer.

In terms of the present invention the term “non-polar thermoplasticelastomer” means that the thermoplastic component is a polyolefinicpolymer including optional additives. Likewise the term “polarthermoplastic polymer” means a thermoplastic polymer which contains inits molecular structure at least one atom selected from nitrogen, oxygenand halogen in addition to carbons and hydrogens.

The term “non-polar thermoplastic elastomer” also extends to blends ofdifferent but compatible non-polar thermoplastic elastomers. Likewisethe term “polar thermoplastic polymer” as used in the description andthe claims also extends to blends of different but compatible polarthermoplastic polymers.

Of course, the compatibilized blend may contain optional additives whichcan be added to blend as such or as additives of its constituents.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

1. Non-polar Thermoplastic Elastomer

The term “thermoplastic elastomer” (TPE) in general defines blends ofpolyolefins and rubbers in which blends the rubber phase is not cured,i.e., so called thermoplastic olefins (TPO), blends of polyolefins andrubbers in which blends the rubber phase has been partially or fullycured by a vulcanization process to form thermoplastic vulcanizates(TPV), or unvulcanized block-copolymers or blends thereof.

According to the present invention the non-polar thermoplastic elastomeris selected from

(A)

(a) a thermoplastic polyolefin homopolymer or copolymer, and

(b) an olefinic rubber which is fully crosslinked, partially crosslinkedor not crosslinked, and optionally

(c) common additives;

(B)

(a) a block-copolymer of styrene/conjugated diene/styrene and/or itsfully or partially hydrogenated derivative, optionally compounded with

(b) a thermoplastic polyolefin homopolymer or copolymer and/or

(c) common additives and

(C) any blend of (A) and (B).

1.1 Non-polar Thermoplastic Elastomer (A)

1.1.1 Thermoplastic Polyolefin

Polyolefins suitable for use in the compositions (A), (B) or (C) of theinvention include thermoplastic, crystalline polyolefin homopolymers andcopolymers. They are desirably prepared from monoolefin monomers having2 to 7 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene,1-pentene, 1-hexene, 1-octene, 3-methyl-1-pentene, 4-methyl-1-pentene,5-methyl-1-hexene, mixtures thereof and copolymers thereof with(meth)acrylates and/or vinyl acetates. Preferred, however, are monomershaving 3 to 6 carbon atoms, with propylene being preferred. As used inthe specification and claims the term polypropylene includeshomopolymers of propylene as well as reactor and/or random copolymers ofpolypropylene which can contain about 1 to about 30 wt % of ethyleneand/or an a-olefin comonomer of 4 to 16 carbon atoms, and mixturesthereof. The polypropylene can be highly crystalline isotactic orsyndiotactic polypropylene. Commercially available polyolefins may beused in the practice of this invention. Further polyolefins which can beused in terms of the invention are high, low, linear-low, verylow-density polyethylenes and copolymers of ethylene with(meth)acrylates and/or vinyl acetates.

The polyolefins mentioned above can be made by conventionalZiegler/Natta catalyst-systems or by single-site catalyst-systems.

The amount of polyolefin found to provide useful compositions (A) isgenerally from about 8 to about 90 weight percent, under the provisothat the total amount of polyolefin (a) and rubber (b) is at least about35 weight percent, based on the total weight of the polyolefin (a),rubber (b) and optional additives (c). Preferably, the polyolefincontent will range from about 10 to about 60 percent by weight.

1.1.2 Olefinic Rubber

Suitable monoolefin copolymer rubbers comprise non-polar, rubberycopolymers of two or more (α-monoolefins, preferably copolymerized withat least one polyene, usually a diene. Saturated monoolefin copolymerrubber, for example ethylene-propylene copolymer rubber (EPM) can beused. However, unsaturated monoolefin rubber such as EPDM rubber is moresuitable. EPDM is a terpolymer of ethylene, propylene and anon-conjugated diene. Satisfactory non-conjugated dienes include5-ethylidene-2-norbomene (ENB); 1,4-hexadiene; 5-methylene-2-norbomene(MNB); 1,6-octadiene; 5-methyl-1,4-hexadiene;3,7-dimethyl-1,6-octadiene; 1,3-cyclopentadiene; 1,4-cyclohexadiene;dicyclopentadiene (DCPD) and vinyl norbomene (VNB).

Butyl rubbers are also useful in the compositions of the invention. Asused in the specification and claims, the term “butyl rubber” includescopolymers of an isoolefin and a conjugated monoolefin, terpolymers ofan isoolefin with or without a conjugated monoolefin, divinyl aromaticmonomers and the halogenated derivatives of such copolymers andterpolymers.

The useful butyl rubber copolymers comprise a major portion of isoolefinand a minor amount, usually less than about 30 wt %, of a conjugatedmultiolefin. The preferred copolymers comprise about 85-99.5 wt % of aC₄₋₇ isoolefin such as isobutylene and about 15-0.5 wt % of amultiolefin of 4-14 carbon atoms, such as isoprene, butadiene, dimethylbutadiene and piperylene. Commercial butyl rubber, chlorobutyl rubber,bromobutyl rubber, useful in the invention, are copolymers ofisobutylene and minor amounts of isoprene with less than about 3%halogen for the halobutyl-derivatives. Other butyl co- and terpolymerrubbers are illustrated by the description in U.S. Pat. No. 4,916,180,the disclosure of which is incorporated herein by reference.

Another suitable copolymer within the scope of the olefinic rubber ofthe present invention is a copolymer of a C₄₋₇ isomonoolefin and apara-alkylstyrene, and preferably a halogenated derivative thereof. Theamount of halogen in the copolymer, predominantly in thepara-alkylstyrene, is from about 0.1 to 10 wt %. A preferred example isthe brominated copolymer of isobutylene and para-methylstyrene. Thesecopolymers are more fully described in U.S. Pat. No. 5,162,445, thedisclosure of which is incorporated herein by reference.

A further olefinic rubber suitable in the invention is natural rubber.The main constituent of natural rubber is the linear polymercis-1,4-polyisoprene. It is normally commercially available in the formof smoked sheets and crepe. Synthetic polyisoprene can also be used.Furthermore polybutadiene rubber and styrene-butadiene-copolymer rubberscan also be used.

Blends of any of the above olefinic rubbers can be employed, rather thana single olefinic rubber.

Further suitable rubbers are nitrite rubbers. Examples of the nitrilegroup-containing rubber include a copolymer rubber comprising anethylenically unsaturated nitrile compound and a conjugated diene.Further, the copolymer rubber may be one in which the conjugated dieneunits of the copolymer rubber are hydrogenated. Specific examples of theethylenically unsaturated nitrile compound include acrylonitrile,α-chloroacrylonitrile, α-fluoroacrylonitrile and methacrylonitrile.Among them, acrylonitrile is particularly preferable.

Examples of the conjugated diene include 1,3-butadiene,2-chlorobutadiene and 2-methyl-1,3-butadiene (isoprene). Among them,butadiene is particularly preferable. Especially preferred nitriterubbers comprise copolymers of 1,3-butadiene and about 10 to about 50percent of acrylonitrile.

Other suitable rubbers in terms of the present invention are based onpolychlorinated butadienes such as polychloroprene rubber. These rubbersare commercially available under the trade names Neoprene® andBayprene®.

In preparing the compositions of the invention, the amount of rubber incomposition (A) generally ranges from about 70 to about 10 weightpercent, under the proviso that the total amount of polyolefin (a) andrubber (b) is at least about 35 weight %, based on the weight of thepolyolefin (a), the rubber (b) and the optional additives (c).Preferably, the olefinic rubber content will be in the range of fromabout 50 to about 10 weight percent.

1.1.3 Vulcanization

If cured, the process of dynamically curing the rubber in the polyolefinmatrix is employed. The process of dynamically curing the rubber in apolyolefin matrix is well known in the art. Early work found in U.S.Pat. No. 3,037,954 discloses the technique of dynamic vulcanizationwherein a vulcanizable elastomer is dispersed into a resinousthermoplastic polymer and the elastomer is cured in the presence of acurative while continuously mixing and shearing the polymer blend. Theresulting composition [dynamically vulcanized alloy, or thermoplasticvulcanizate (TPV)] is a microgel dispersion of cured elastomer in anuncured matrix of thermoplastic polymer. Since then the technology hasadvanced significantly. For further general background information it isreferred to EP-A-0 473 703, EP-A-0 657 504, WO-A-95/25380 and otherpatent applications of the applicant the disclosure of which isincorporated herein by reference.

The elastomer (rubber) component of the TPV can be uncured, partially orfully vulcanized (crosslinked). Those ordinarily skilled in the art willappreciate the appropriate quantities, types of cure systems andvulcanization conditions required to carry out the vulcanization of therubber. The elastomer can be vulcanized using varying amounts ofcurative, varying temperatures and varying time of cure in order toobtain the optimum crosslinking desired. Any known cure system can beused, so long as it is suitable under the vulcanization conditions forthe elastomer or combination of elastomers being used and is compatiblewith the thermoplastic polyolefin component of the TPV. These curativesinclude sulfur, sulfur donors, metal oxides, phenolic resin systems,maleimides, peroxide-based systems, high energy radiation and the like,both with and without accelerators and co-agents. Another curing systemwhich can be used is the hydrosilylation system which consists of theuse of a silicon hydride curative catalyzed with a platinum or rhodiumderivative. Such systems are disclosed, for instance, in EP-A-0776937.Phenolic resin curatives are preferred for the preparation of the TPVcomposition of the invention, and such cure systems are well known inthe art and literature of vulcanization of elastomers. Their use in TPVcompositions is more fully described in U.S. Pat. No. 4,311,628, thedisclosure of which is fully incorporated herein by this reference.Usually 5 to 20 weight parts of the curative or curative system are usedper 100 weight parts of the rubber to be cured.

1.2 Thermoplastic Elastomer (B)

Another thermoplastic elastomer (B) is a block-copolymer ofstyrene/conjugated diene/styrene, with the conjugated diene optionallybeing fully or partially hydrogenated, or mixtures thereof. Generallythis block-copolymer may contain about 10 to about 50 weight %, morepreferably about 25 to about 35 weight % of styrene and about 90 toabout 50 weight %, more preferably about 75 to about 35 weight % of theconjugated diene, based on said block-copolymer. Most preferably,however, is a block-copolymer which contains about 30 weight % ofstyrene and about 70 weight % of the conjugated diene. The conjugateddiene is selected from butadiene, isoprene or mixtures thereof. Specificblock-copolymers of the styrene/conjugated diene/styrene-type are SBS,SIS, SIBS, SEBS and SEPS block-copolymers. These block-copolymers areknown in the art and are commercially available.

Optionally the block-copolymer may further be compounded with apolyolefin or a common additive or mixtures thereof. Thus, thethermoplastic elastomer (B) optionally further comprises up to about 60weight % of (b) the thermoplastic polyolefin homopolymer or copolymer orthe additives or mixtures thereof, based on the total weight of theblock-copolymer (a) and (b). Preferably, the thermoplastic elastomer (B)comprises at least 10 weight % of the thermoplastic polyolefin. Thethermoplastic polyolefins are selected from those mentioned above incontext with the thermoplastic elastomer (A).

1.3 Thermoplastic Elastomer (C)

Other thermoplastic elastomers which can be modified with modifiermentioned herein below are blends of the thermoplastic elastomer (A)comprising the polyolefin, rubber and optionally additives with thethermoplastic elastomer (B) comprising the block-copolymer, optionallypolyolefins and/or additives.

Preferred blends (C) contain about 5 to about 95 weight % of (A) andabout 95 to about 5 weight % of (B) respectively, based on the totalamount of (A) and (B). These blends can be prepared by commonblending-processes known in the art.

2. Polar Thermoplastic Polymer

According to the present invention the polar thermoplastic polymer isselected from thermoplastic polyurethanes (TPU), chlorine containingpolymers, for instance, polyvinylidene chloride (PVDC),polyvinylchloride (PVC), chlorinated polyethylene (CPE), fluorinecontaining polymers, for instance, polyvinylidene fluoride (PVDF),polyesters, acrylonitrile-butadiene-styrene copolymer (ABS),styrene-acrylonitrile copolymer (SAN), styrene-maleic anhydridecopolymer (SMA), polyacetals, polycarbonates, polyphenylene oxide.

2.1 Thermoplastic Polyurethane (TPU)

The polyurethane component has no limitation in respect of itsformulation other than the requirement that it be thermoplastic innature which means that it is prepared from substantially difunctionalingredients, i.e., organic diisocyanates and components beingsubstantially difunctional in active hydrogen containing groups.

However, often times minor proportions of ingredients withfunctionalities higher than 2 may be employed. This is particularly truewhen using extenders such as glycerol, trimethylol propane, and thelike. Such thermoplastic polyurethane compositions are generallyreferred to as TPU materials. Accordingly, any of the TPU materialsknown in the art can be employed within the scope of the presentinvention. For representative teaching on the preparation of TPUmaterials see Polyurethanes: Chemistry and Technology, Part II, Saundersand Frisch, 1964, pp 767 to 769, Interscience Publishers, New York, N.Y.and Polyurethane Handbook, Edited by G. Oertel 1985, pp 405 to 417,Hanser Publications, distributed in U.S.A. by Macmillan Publishing Co.,Inc., New York, N.Y. For particular teaching on various TPU materialsand their preparation see U.S. patent publications U.S. Pat. Nos.2,929,800; 2,948,691; 3,493,634; 3,620,905; 3,642,964; 3,963,679;4,131,604; 4,169,196; Re 31,671; 4,245,081; 4,371,684; 4,379,904;4,447,590; 4,523,005; 4,621,113; 4,631,329; and 4,883,837, thedisclosure of which is incorporated herein by reference.

The preferred TPU is a polymer prepared from a mixture comprising atleast one organic diisocyanate, at least one polymeric diol and at leastone difunctional extender. The TPU may be prepared by the prepolymer,quasi-prepolymer, or one-shot methods in accordance with the methodsdescribed in the references cited above.

Any of the organic diisocyanates previously employed in TPU preparationcan be employed including blocked or unblocked aromatic, aliphatic, andcycloaliphatic diisocyanates, and mixtures thereof.

Illustrative isocyanates but non-limiting thereof are methylenebis(phenyl isocyanate) including the 4,4′-isomer, the 2,4′-isomer andmixtures thereof, m- and p-phenylene diisocyanates, chlorophenylenediisocyanates, α,α′-xylylene diisocyanate, 2,4- and 2,6-toluenediisocyanate and the mixtures of these latter two isomers which areavailable commercially, tolidine diisocyanate, hexamethylenediisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate andthe like; cycloaliphatic diisocyanates such as methylene bis(cyclohexylisocyanate) including the 4,4′-isomer, the 2,4′-isomer and mixturesthereof, and all the geometric isomers thereof including trans/trans,cis/trans, cis/cis and mixtures thereof, cyclohexylene diisocyanates(1,2-; 1,3-; or 1,4-), 1-methyl-2,5-cyclohexylene diisocyanate,1-methyl-2,4-cyclohexylene diisocyanate, 1-methyl-2,6-cyclohexylenediisocyanate, 4,4′-isopropylidene bis-(cyclohexyl isocyanate),4,4′-diisocyanato dicyclohexyl, and all geometric isomers and mixturesthereof, and the like. Also included are the modified forms of methylenebis(phenyl isocyanate). By the latter are meant those forms of methylenebis(phenyl isocyanate) which have been treated to render them stableliquids at ambient temperature (about 20° C.). Such products includethose which have been reacted with a minor amount (up to about 0.2equivalents per equivalent of polyisocyanate) of an aliphatic glycol ora mixture of aliphatic glycols such as the modified methylene bis(phenylisocyanates) described in U.S. Pat. Nos. 3,394,164; 3,644,457;3,883,571; 4,031,026; 4,115,429; 4,118,411; and 4,299,347 the disclosureof which is incorporated herein by reference. The modified methylenebis(phenyl isocyanates) also include those which have been treated so asto convert a minor proportion of the diisocyanate to the correspondingcarbodiimide which then interacts with further diisocyanate to formurethane-imine groups, the resulting product being a stable liquid atambient temperatures as described, for example, in U.S. Pat. No.3,384,653. Mixtures of any of the above-named polyisocyanates can beemployed if desired.

Preferred classes of organic diisocyanates include the aromatic andcycloaliphatic diisocyanates. Preferred species within these classes aremethylene bis(phenyl isocyanate) including the 4,4′-isomer, the2,4′-isomer, and mixtures thereof, and methylene bis(cyclohexylisocyanate) inclusive of the isomers described above.

The polymeric diols which can be used are those conventionally employedin the art for the preparation of TPU elastomers. The polymeric diolsare responsible for the formation of soft segments in the resultingpolymer and advantageously have molecular weights (number average)falling in the range of 400 to 4000 and preferably 500 to 3000. It isnot unusual, and, in some cases, it can be advantageous to employ morethan one polymeric diol. Exemplary of the diols are polyether diols,polyester diols, hydroxy-terminated polycarbonates, hydroxy-terminatedpolybutadienes, hydroxy-terminated polybutadiene-acrylonitrilecopolymers, hydroxy-terminated copolymers of dialkyl siloxane andalkylene oxides such as ethylene oxide, propylene oxide and the like,and mixtures in which any of the above polyols are employed as majorcomponent (greater than 50% w/w) with amino-terminated polyethers andamino-terminated polybutadiene-acrylonitrile copolymers.

Illustrative of polyether polyols are polyoxyethylene glycols,polyoxypropylene glycols which, optionally, have been capped withethylene oxide residues, random and block copolymers of ethylene oxideand propylene oxide; polytetramethylene glycol, random and blockcopolymers of tetrahydrofuran and ethylene oxide and/or propylene oxide,and products derived from any of the above reaction with di-functionalcarboxylic acids or ester derived from said acids in which latter caseester interchange occurs and the esterifying radicals are replaced bypolyether glycol radicals. The preferred polyether polyols are randomand block copolymers of ethylene and propylene oxide of functionalityapproximately 2.0 and polytetramethylene glycol polymers offunctionality about 2.0.

Illustrative of polyester polyols are those prepared by polymerizingε-caprolactone using an initiator such as ethylene glycol, ethanolamine,and the like; and those prepared by esterification of polycarboxylicacids such as phthalic, terephthalic, succinic, glutaric, adipic,azelaic, and the like; acids with polyhydric alcohols such as ethyleneglycol, butanediol, cyclohexane dimethanol, and the like.

Illustrative of the amine-terminated polyethers are the aliphaticprimary di-amines structurally derived from polyoxypropylene glycols.Polyether diamines of this type are available from Jefferson ChemicalCompany under the trademark JEFFAMINE®.

Illustrative of polycarbonates containing hydroxyl groups are thoseprepared by reaction of diols such as propane-1,3-diol, butane-1,4-diol,hexane-1,6-diol, 1,9-nonanediol, 2-methyloctane-1,8-diol, diethyleneglycol, triethylene glycol, dipropylene glycol, and the like, withdiarylcarbonates such as diphenylcarbonate or with phosgene.

Illustrative of the silicon-containing polyethers are the copolymers ofalkylene oxides with dialkylsiloxanes such as dimethylsiloxane, and thelike; see, for example, U.S. Pat. Nos. 4,057,595 or 4,631,329 citedsupra.

Illustrative of the hydroxy-terminated polybutadiene copolymers are thecompounds available under the tradename Poly BD Liquid Resins.Illustrative of the hydroxy- and amine-terminatedbutadiene/acrylonitrile copolymers are the materials available under thetrade name HYCAR® hydroxyl-terminated (HT) liquid polymers andamine-terminated (AT) liquid polymers, respectively. Preferred diols arethe polyether and polyester diols set forth above.

The difunctional extender employed can be any of those known in the TPUart disclosed above. Typically the extenders can be aliphatic straightand branched chain diols having from 2 to 10 carbon atoms, inclusive, inthe chain. Illustrative of such diols are ethylene glycol,1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,neopentyl glycol, and the like; 1,4-cyclohexandimethanol; hydroquinonebis-(hydroxy-ethyl)ether, cyclohexylenediols (1,4-, 1,3-, and1,2-isomers), isopropylidene bis(cyclohexanols); diethylene glycol,dipropylene glycol, ethanolamine, N-methyl-diethanolamine, and the like;and mixtures of any of the above. As noted previously, in some casesminor proportions (less than about 20 equivalent percent) of thedifunctional extender may be replaced by trifunctional extenders withoutdetracting from the thermoplasticity of the resulting TPU; illustrativeof such extenders are glycerol, trimethylolpropane, and the like.

While any of the diol extenders described and exemplified above can beemployed alone, or in admixture, it is preferred to use 1,4-butanediol,1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, ethyleneglycol, and diethylene glycol, either alone or in admixture with eachother or with one or more aliphatic diols previously named. Particularlypreferred diols are 1,4-butanediol, 1,6-hexanediol, and1,4-cyclohexanedimethanol.

The equivalent proportions of polymeric diol to said extender can varyconsiderably depending on the desired hardness for the TPU product.Generally speaking, the proportions fall within the respective range offrom about 1:1 to about 1:20, preferably from about 1:2 to about 1:10.At the same time the overall ratio of isocyanate equivalents toequivalents of active hydrogen containing materials is within the rangeof 0.90:1 to 1.10:1, and preferably, 0.95:1 to 1.05:1.

The TPU's can be prepared by conventional methods which are known to theartisan, for instance from U.S. Pat. No. 4,883,837 and the furtherreferences cited therein.

2.2 Chlorine Containing Polymers

The chlorine containing polymers are selected from polyvinylchioride,polyvinylidene copolymer, chlorinated polyvinylchloride, chlorinatedpolyethylene, and the like.

2.3 Fluorine Containing Polymers

The fluorine containing polymers are selected from polyvinylidenefluoride, vinylidene fluoride-hexafluoropropylene copolymer, and thelike.

2.4 Polyester

In terms of the present invention any commercial thermoplastic polyestersuch as polyethylene terephthalate, polybutylene terephthalate,saturated or unsaturated aliphatic polyesters, and the like can be used.

3. Compatibilizer

According to the present invention the compatibilizer is selected from

(i) a copolymer obtainable by condensation reaction of

about 10 to about 90 weight % of a functionalized polymer with

about 90 to about 10 weight % of a polyamide, based on the total weightof functionalized polymer and polyamide, or

(ii) a blend of functionalized polymer and a polyamide in the amountsdefined under (i) or

(iii) a mixture of (i) and (ii), under the proviso that thefunctionalized polymer contains not less than about 0.3 weight % basedon the total weight of the functionalized polymer, at least onefunctional group containing comonomer.

The compatibilizer is added to the blend of the non-polar thermoplasticelastomer and the polar thermoplastic polymer in an amount of at least 1part by weight, preferably 3 to 40 parts by weight and most preferably 5to 20 parts by weight based on 100 weight parts of the blend comprisingthe non-polar thermoplastic elastomer and the polar thermoplasticpolymer.

According to the present invention the functionalized polymer used inthe compatibilizer is selected from functionalized polyolefins andfunctionalized block-copolymers of styrene/conjugated diene/styrene. Inthe functionalized block-co-polymers of styrene/conjugated diene/styrenethe conjugated diene may be hydrogenated, non-hydrogenated or partiallyhydrogenated.

The presence of a copolymer of functionalized polymers and polyamide inthe thermoplastic elastomers significantly improves the compatibility ofnon-polar thermoplastic elastomers with polar thermoplastic polymers.The copolymers of functionalized polymers and polyamides can be preparedby condensation reaction of functionalized polymers and polyamides. Thistype of reaction is known to those skilled in the art (F. Ide and A.Hasegawa, J. Appl. Polym. Sci., 18 (1974) 963; S. Hosoda, K. Kojima, Y.Kanda and M. Aoyagi, Polym. Networks Blends, 1 (1991) 51; S. J. Park, B.K. Kim and H. M. Heong, Eur. Polym. J., 26 (1990)131). The reactionsdescribed in these references can easily be transferred to the otherfunctionalized polymers mentioned below.

The polyolefins of the functionalized polyolefins include thermoplastic,crystalline polyolefin homopolymers and copolymers. They are desirablyprepared from α-monoolefin monomers having 2 to 7 carbon atoms such asethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene,1-octene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene,mixtures thereof and copolymers thereof with (meth)acrylates and/orvinyl acetates. Preferred, however, are monomers having 3 to 6 carbonatoms, with propylene being preferred. As used in the specification andclaims the term polypropylene includes homopolymers of propylene as wellas reactor copolymers of polypropylene which can contain 1 to 20 weight% of ethylene or an α-olefin comonomer of 4 to 16 carbon atoms, andmixtures thereof. The polypropylene can be highly crystalline isotacticor syndiotactic polypropylene. Commercially available polyolefins may beused in the practice of the invention. Further preferable among thepolyolefins are low-density polyethylene, linear low-densitypolyethylene, medium- and high-density polyethylene, polypropylene, andpropylene-ethylene random or block co-polymers as well asethylene-vinylacetate copolymer (EVA), ethylene-acrylic acid copolymer(EAA) and their ionomeric derivatives, such as the Zn- and Na-containingsalts, and ethylene-(meth)acrylate copolymer, such as EMA.

In the block-copolymers of styrene/conjugated diene/styrene, which aretraditionally made by anionic polymerization and in which the conjugateddiene may be hydrogenated, non-hydrogenated or partially hydrogenated,the conjugated diene is selected from butadiene, isoprene or a mixtureof both. Specific block-copolymers of the styrene/conjugateddiene/styrene-type are SBS, SIS, SIBS, SEBS and SEPS block-copolymers.

The functionalized polymers contain one or more functional groups whichhave been incorporated either by grafting or by copolymerization.Preferably the functionalized polymers used in this invention are thoseobtained by grafting at least one kind of functional group-containingmonomer on the polymer backbone, which is, as mentioned above, selectedfrom the polyolefins or the block-copolymers. It is preferred, however,to use one kind of functional group-containing monomer. The functionalgroup-containing monomers are selected from carboxylic acids,dicarboxylic acids, their derivatives such as their anhydrides,oxazoline- or epoxy-group containing monomers, or amino- orhydroxy-group containing monomers.

Examples of the monomers containing one or two carboxylic groups arethose having 3 to 20 carbon atoms per molecule such as acrylic acid,methacrylic acid, maleic acid, fumaric acid and itaconic acid orderivatives thereof.

Unsaturated dicarboxylic acid monomers having 4 to 10 carbon atoms permolecule and anhydrides (if they exist) thereof are the preferredgrafting monomers. These grafting monomers include for example, maleicacid, fumaric acid, itaconic acid, citra-conic acid,cyclohex4-ene-1,2-dicarboxylic acid,bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, maleic anhydride,itaconic anhydride, citraconic anhydride, allyl-succinic anhydride,4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride andbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, and the like.

Examples of oxazoline-group containing monomers are oxazole,ricinoloxazoline maleinate, vinyloxazoline, 2-isopropenyl-2-oxazoline,and the like.

Examples of epoxy-group containing monomers are epoxides of esters ofunsaturated carboxylic acids containing at least 6, preferably 7 carbonatoms. Particularly preferred are glycidyl acrylate and glycidylmethacrylate, and the like.

Examples of the amino-group containing monomers are reaction-products ofprimary and/or secondary diamines with an anhydride of an unsaturatedcarboxylic acid as mentioned above.

Examples of the hydroxy-group containing monomers are reaction productsof primary or secondary amino-alcohols (primary or secondary amine) withan anhydride of an unsaturated carboxylic acid as mentioned above.

In case that an amine or hydroxy group is present in the resultingfunctionalized polymer a coupling agent such as an diisocyanate could benecessary to link this type of functional polymer to the polyamide.

Various known methods can be used to graft the grafting monomer to thebasic polymer. For example, this can be achieved by heating the polymerand the grafting monomer at high temperatures of from about 150° C. toabout 300° C. in the presence or absence of a solvent with or without aradical initiator. Another vinyl monomer may be present during thegrafting reaction. Suitable solvents that may be used in this reactioninclude benzene, toluene, xylene, chlorobenzene and cumene. Suitableradical initiators that may be used include t-butyl hydroperoxide,diisopropylbenzene hydroperoxide, di-t-butyl peroxide, t-butyl cumylperoxide, acetyl peroxide, benzoyl peroxide, isobutyryl peroxide andmethylethyl ketone peroxide, and the like.

The functionalized polymer can also be made by copolymerization of thefunctional group-containing monomer with the monomers mentioned above inconnection with the polyolefins.

In the functionalized polymer thus obtained, the amount of thefunctional group-containing monomer is preferably about 0.3 to about10%, more preferably about 0.3 to about 5%, and most preferably at leastabout 1 weight %, based on the weight of the functionalized polymer.

The polyamides are preferably selected from polymers of ε-caprolactam,aminocaproic acid, enantholactam, 7-amino-heptanoic acid,11-aminoundecanoic acid, etc., or polymers obtained by polycondensationof diamines (such as butanediamine, hexamethylenediamine,nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine,m-xylenediamine, etc.) with dicarboxylic acids (such as terephthalicacid, isophthalic acid, adipic acid, sebacic acid, dodecanedibasic acid,glutaric acid, etc.), copolymers thereof or blends thereof. Specificexamples include aliphatic polyamide resins (such as polyamide 4.6,polyamide 6, polyamide 6.6, polyamide 6.10, polyamide 11, polyamide 12,and polyamide 6.12) and aromatic polyamide resins (such aspoly(hexamethylenediamine terephthalamide), poly(hexamethyleneisophthalamide), xylene group-containing polyamides and amorphouspolyamide). Among them, polyamide 6, polyamide 6.6, and polyamide 12 arepreferred.

It has to be noted that the copolymer of the functionalized polymer andthe polyamide can first be prepared as such (e.g. in a single or atwin-screw extruder) and then melt-mixed or dry-blended with thenon-polar thermoplastic elastomer and polar thermoplastic compositionbefore processing. Alternatively, the functionalized polymer andpolyamide can be melt-mixed with the non-polar thermoplastic elastomerand polar thermoplastic composition in one step. The compatibilizer canbe also dry-blended or melt-mixed with either non-polar thermoplasticelastomer or with polar thermoplastic. The melt-mixing of the lastoption can be made either down-stream during manufacturing of thenon-polar thermoplastic elastomer or in a second pass in a Banbury,single or double screw extruder.

Preferably the amount of the functionalized polymer is about 20 to about70 weight % and the amount of the polyamide is about 80 to about 30weight %. Most preferably, however, the amount of the functionalizedpolymer is about 30 to about 60 weight % and the amount of the polyamideis about 70 to about 40 weight %, all amounts based on the total weightof the functionalized polymer and polyamide.

The amount of copolymer obtainable by the reaction of the functionalizedpolyolefin and the polyamide and the amount of copolymer obtainable bythe reaction of the functionalized styrene/conjugated diene/styreneblock-copolymer (hydrogenated, non-hydrogenated or partly hydrogenated)and the polyamide in the blend comprising the non-polar thermoplasticelastomer and the polar thermoplastic polymer, whether added to saidblend as the copolymer (already reacted) or as blend (not yet reacted)as above-described, is at least 3 weight parts [(i), (ii) or (iii)] per100 weight parts of the total of non-polar thermoplastic elastomer (A),(B) or (C), and polar thermoplastic polymer as defined above.

4. Additives

The non-polar thermoplastic elastomer, the polar thermoplastic polymer,the compatibilizer and the final compatibilized blend may independentlycontain reinforcing and non-reinforcing fillers, plasticizers,antioxidants, stabilizers, rubber processing oil, extender oils,lubricants, antiblocking agents, antistatic agents, waxes, foamingagents, pigments, flame retardants and other processing aids known inthe rubber compounding art. Such additives can comprise up to about 40wt %, preferably up to 20 wt % of the total compatibilized blend.Fillers and extenders which can be utilized include conventionalinorganics such as calcium carbonate, clays, silica, talc, titaniumdioxide, carbon black, and the like. The rubber processing oilsgenerally are paraffinic, naphthenic or aromatic oils derived frompetroleum fractions. The oils are selected from those ordinarily used inconjunction with the specific rubber or rubbers present in thecomposition.

5. Preparation of the Compatibilized Blend

The compatibilized blends of a non-polar thermoplastic elastomer andpolar thermo-plastic comprising the compatibilizer copolymer areprepared by melt-mixing the polymers together in the presence of thecompatibilizer in a conventional internal mixer, a single screwextruder, a co- or counter-rotation twin-screw extruder, an open mill orany other type of equipment suitable and known in the art. The mixtureis heated to a temperature sufficient to melt or to soften the componentof the composition which has the highest melting or softening point.

The compatibilizer can be first melt-mixed or tumble blended with thenon-polar thermoplastic elastomer or with the polar thermoplastic andthen melt-mixed with the second component of the composition.

6. Utility of the Compatibilized Blend

The compatibiiized blends of non-polar thermoplastic elastomer and polarthermo-plastic according to the present invention can be used indifferent applications like:

i. to get good adhesion between the compatibilized blend of theinvention and polar thermoplastic polymers which is necessary if, forinstance, parts with a multilayer structure are provided. This type ofparts can be produced by using the traditional processing methods suchas co-injection molding and/or over injection molding, co-extrusionand/or over extrusion, co-blow molding and/or over blow molding.

Representative polar thermoplastic polymers are selected from thosementioned above.

In all cases mentioned above, the compatibilized blend of the inventioncan also be used as an adhesive tie layer between a non-polarthermoplastic elastomer and a polar thermoplastic polymer.

ii. to improve the paintability of non-polar thermoplastic elastomers;

iii. to produce new polymer materials which possess the combinedproperties of non-polar thermoplastic elastomer and polar thermoplasticpolymers.

The invention will better be understood by reference to the followingexamples which serve to illustrate but not to limit the presentinvention.

EXAMPLES

The following abbreviations are used in the examples:

S 8211-60: Santoprene® rubber (blend of polypropylene and fullyvulcanized EPDM and common additives with a durometer shore A hardnessof 60), [Advanced Elastomer Systems, Akron, Ohio, U.S.]

S 691-55: Santoprene® rubber (blend of polypropylene and fullyvulcanized EPDM and common additives with a durometer shore A hardnessof 55), [Advanced Elastomer Systems, Akron, Ohio, U.S.].

PP-b-PA reaction product of maleated polypropylene having 1.1% graftedmaleic anhydride with polyamide 6 (Ultramid® B3 of BASF) at 40/60 weight%

Solef® 11010: Polyvinylidene fluoride-hexafluoropropylene copolymer[Solvay]

Elastollan® C 85 A (TPU): thermoplastic polyurethane based on polyether[BASF]

The following measurement methods were used in the determination ofphysical properties:

Hardness (Shore A): ISO 868-85

Modulus; Elongation and Tensile Strength: DIN 53405

Tear Strength: ASTM D-624

Typical Examples

1. Preparation of the Compatibilizer (PP-b-PA)

40 weight % of a maleated homo-polypropylene containing 1.1 weight % ofgrafted maleic anhydride was melt-mixed with 60 weight % of polyamide 6(Ultramid® B3 of BASF) in a co-rotating intermeshing twin-screw extrudertype Leistritz LSM 33/34.

The following temperature setting profile has been used:

Zone 1 and 2 229° C. Zone 3 and 4 230° C. Zone 5 231° C. Zone 6 to 10232° C.

An under-water strand cutting system was used for the pelletization ofthe compatibilizer thus obtained.

2. Preparation of a Compatibilized Blend of a Non-polar ThermoplasticElastomer with a Polar Thermoplastic Polymer

S8211-60, PVDF Solef 11010 and the compatibilizer was firsttumble-blended and then fed into a laboratory single extruder. Extrusiongraph type 19/25 D with metering screw (screw with mixing element) withthe following temperature setting profile:

180° C. (feeding zone)-190-210-200 (die).

Melt-temperature (actual measurement)=250° C.

RPM=70

Back pressure=20 bars

The final product is pelletized through an under water strand cuttingsystem.

TABLE 1 Composition 1 2* S 8211-60 70 70 PP-b-PA (40/60) 10 — Solef11010 20 30 Hardness (5 sec.) Shore A 87 — Direction ⊥ to flow Mod. at100% (MPa) 4.4 — Elongation at Break (%) 234 — Tensile at Break (MPa)4.9 — Direction ∥ to flow Mod. at 100% (MPa) 4.6 — Elongation at Break(%) 274 — Tensile at Break (MPa) 5.2 — Tear (N/mm) direction ⊥ to flow34 — direction ∥ to flow 36 — *Product was not processable due to astrong delamination

TABLE 2 Composition 3 4 S 691-55 70 80 Elastollan ® C 85A (TPU) 30 20PP-b-PA (40/60) 10 — Hardness (5 sec.) Shore A 77 65 Direction ⊥ to flow(DIN 53505) Mod. at 100% (MPa) 3.8 2.1 Elongation at Break (%) 320 223Tensile (MPa) 6.4 2.9 Direction ∥ to flow Mod. at 100% (MPa) 3.3 2.6Elongation at Break (%) 260 185 Tensile (MPa) 4.9 3.1 Tear Strength/N/mm) (ASTM D624) Direction ⊥ to flow 31.5 19.7 Direction ∥ to flow29.4 19.2 Comment on injection molded plaque — delamination

A comparison of inventive example 3 with comparative example 4 showsthat the final product of example 4 has poor physical properties due todelamination caused by non-compatibility of the non-polar thermoplasticelastomer (S 691-55) with the polar thermoplastic polymer (Elastollan®).

I claim:
 1. A compatibilized blend comprising: A) a non-polarthermoplastic elastomer comprising a thermoplastic polyolefinhomopolymer or copolymer and an olefin rubber which is fully crosslinkedor partially crosslinked; and B) a polar thermoplastic polymer selectedfrom the group consisting of thermoplastic polyurethane (TPU), chlorocontaining polymers, fluoro containing polymers, polyesters,acrylonitrile-butadiene-styrene copolymers, styrene-acrylonitrilecopolymers, styrene-maleic anhydride copolymer, polyacetal,polycarbonate, and polyphenylene oxide; and C) a compatibilizer selectedfrom the group consisting of a) a condensation copolymer of 10 to 90weight % of a functionalized olefin polymer with 90 to 10 weight % of apolyamide, based on the total weight of functionalized polymer andpolyamide, or b) a blend of a functionalized olefin polymer and apolyamide in the amounts defined under (a) or c) a mixture of (a) and(b), under the proviso that the functionalized polymer contains no lessthan 0.3 weight %, based on the total weight of the functionalizedpolymer, of at least one functional group-containing monomer.
 2. Theblend of claim 1, wherein at least 1 weight part of the compatibilizer(C) is added per 100 weight parts of the blend comprising the non-polarthermoplastic elastomer (A) and the polar thermoplastic polymer (B). 3.The blend of claim 1, wherein the thermoplastic polyolefin of (A) is ahomopolymer or copolymer of a C₂₋₇ monomer or a copolymer thereof with(meth)acrylates and/or vinyl acetates.
 4. The blend of claim 3, whereinthe copolymer is a copolymer of ethylene with (meth)acrylates and/orvinyl acetates.
 5. The blend of claim 1, wherein the rubber is selectedfrom the group consisting of EPDM rubber, EPM rubber, butyl rubber,halogenated butyl rubber, copolymers of isomonoolefin andpara-alkylstyrene or their halogenated derivatives, natural rubber,polyisoprene, polybutadiene rubber, styrene-butadiene-copolymer rubbers,nitrile rubbers, polychloroprene rubbers and mixtures thereof.
 6. Theblend of claim 1, wherein the blend comprising (A) and (B) containsabout 5 to about 95 weight % of (A), based on the total weight of(A)+(B).
 7. The blend of claim 1, wherein the functionalized olefinpolymers are obtained by grafting on the polyolefins grafting monomersselected from the group consisting of carboxylic acids, dicarboxylicacids or their derivatives, oxazoline-group containing monomers,epoxy-group containing monomers, and amino- or hydroxy-group containingmonomers.
 8. The blend of claim 7, wherein the derivatives of thedicarboxylic acid monomers are their anhydrides.
 9. The blend of claim1, wherein the thermoplastic polyurethane is obtained by the reaction ofat least one organic diisocyanate, at least one polymeric diol and atleast one difunctional chain extender.
 10. A shaped article comprisingthe blend as defined in claim
 1. 11. A method of compatibilizing blendscomprising blending A) a non-polar thermoplastic elastomer comprising athermoplastic polyolefin homopolymer or copolymer and an olefin rubberwhich is fully crosslinked or partially crosslinked; and B) a polarthermoplastic polymer selected from the group consisting ofthermoplastic polyurethane (TPU), chloro containing polymers, fluorocontaining polymers, polyesters, acrylonitrile-butadiene-styrenecopolymers, styrene-acrylonitrile copolymers, styrene-maleic anhydridecopolymer, polyacetal, polycarbonate, and polyphenylene oxide, with acompatibilizer selected from the group consisting of a) a copolymerobtained by condensation reaction of 10 to 90 weight % of afunctionalized olefin polymer with 90 to 10 weight % of a polyamide,based on the total weight of functionalized polymer and polyamide, or b)a blend of a functionalized olefin polymer and a polyamide in theamounts defined under (a) or c) a mixture of (a) and (b), under theproviso that the functionalized polymer contains no less than 0.3 weight%, based on the total weight of the functionalized polymer, of at leastone functional group-containing monomer.